Lubricant additive and composition containing same



United Stat P e 3,002,925 LUBRICANT ADDITIVE AND COMPOSITION CONTAINING SAME Albert R. Sabol, Munster, -Eli W. Blaha, Highland, and Robert E. Karll, Munster, Ind., assignors to Standard Oil Company, Chicago, lll.,-a corporation of Indiana No Drawing. Filed May 26, 1958, Ser. No. 737,480 15 Claims. (Cl. 25232.7)

The present invention relates to an improved lubricant additive, and lubricant compositions containing the same, and more particularly relates to an oil-soluble alkaline earth and boron complex of the reaction product of a phosphorus sulfide and a hydrocarbon containing a high percent of the alkaline earth metal, and to lubricant compositions containing the improved lubricant additive.

' Neutralized reaction products of a phosphorus sulfide anda hydrocarbon, particularly olefin polymer, are widely used as detergent-type'additives in lubricant, especially in crankcase lubricating oils of internal combustion engines. The use of such additives in'lubricant compositions is described in US. Patents No. 2,316,080, and No. 2,316,082, issued April 6, 1943, to C. M. Loane et al. Such detergent-type additives are most effective under heavy duty, high temperature conditions of engine operation. However, in engines operating undermoderate or light duty service and under intermittent operating conditions, wherein low engine jacket andv crankcase temperatures prevail, such detergent additives often are of limited effectiveness in combating sludge conditions of the lowtemperature type which may result from extreme oil contamination with combustion chamber blow-by products. For such low temperature operating conditions lubricant detergent-type additives of higher ratios of alkaline earth metal to phosphorus are desired. Also, it is desirable to provide a low-temperature detergent-type additive which is effective in preventing the corrosion of copper and silver which are components of bearings, etc. in present day internal combustion engines.

It is an object of the present invention to provide a method of preparing an improved lubricating oil lowtemperature detergent-type additive having a high alkaline earth metal to phosphorus ratio. Another object is to provide a lubricating oil additive having a high alkaline earth metal to phosphorus ratio and which possesses detergency and corrosion-inhibiting properties. Another object of the invention is to provide an alkaline earthcontaining neutralized reaction product of a phosphorus sulfide and a hydrocarbon having a high alkaline earth content, and having detergency and silver and/or copper corrosion-inhibiting properties. Still another object of the invention is to provide a lubricant composition containing the improved additive. Other objects and advantages of the invention will become apparent from the following description thereof.

In accordance with the present invention, the foregoing objects are attained by they use of an oil-soluble additive complex obtained by reacting a phosphorus sulfide, e.g. phosphorus pentasulfide, with a normally non-gaseous hydrocarbon, as hereinafter'described, under conditions to avoid hydrolysis of said reaction product, and subsequently forming a complex by reacting the unhydrolyzed reaction product with boric acid, anhydride or ester and a basic alkaline earth compound in the presence of water and an alkanol of 1 to 3 carbon atoms under the hereinafter described conditions.

In the preparation of the phosphorus sulfide-hydro. carbon reaction product, the hydrocarbon isreacted with a phosphorus sulfide, such as P 8 P 8 P 87 or other phosphorus sulfides, and preferably phosphorus pentasul fide, P 8

The hydrocarbon constituent ofthis reaction is suitably a normally non-gaseous hydrocarbon such as is described in detail in US. 2,316,080, 2,316,082, and 2,316,088, each issued to Loane et al. on April 6, 1943. While the hydrocarbon constituent of this reaction can be any of the type hereinafter described, it is preferably a mono-olefin hydro carbon polymer resulting from the polymerization of low molecular weight mono-olefinic hydrocarbons or isomono olefinic hydrocarbons, such as propylene, butylenes, and amylenes or the copolyme'rs obtained by the polymerization of hydrocarbon mixtures containing isomono-olefins and mono-olefins or mixtures of olefins in the presence of a catalyst, such as sulfuric acid, phosphoric acid, boron fluoride, aluminum chloride or other similar halide catae lysts of the Friedel-Crafts type. I

The polymers employed are preferably mono-olefin polymers or mixtures of mono-olefin polymers and isomono-olefin polymers having molecular weights ranging from about 150 to about 50,000 or more, and preferably from about 300 to about 10,000. Such polymers can be obtained, for example, by the polymerization in the liquid phase of a hydrocarbon mixture containing mono-olefins and isomono-olefins such as butylene and isobutylene at a temperature of from'about F. to about F. in the presence of a metal halide catalyst of the Friede'l- Crafts types such as, for example, boron fluoride, aluminum chloride, and the like. In the preparation of these polymers we may employ, for example, a hydrocarbon mixture containing isobutylene, butylenes and butanes recovered from petroleum gases, especially those gases produced in the cracking of petroleum oils in the manufacture of gasoline.

Essentially paraflinic hydrocarbons such as bright stock r'esiduums, lubricating oil distillates, petrolatums, or paraffin waxes, may be used. There can also be employed the condensation products of any of the foregoing hydrocarbons, usually through first halogenating the hydrocarborn, with aromatic hydrocarbons in the presence of anhydrous inorganic halides, such as aluminum chloride, zinc chloride, boron fluoride, and the like.

Other preferred olefins suitable for the preparation of the herein described phosphorus sulfide reaction products are olefins having at least 20 carbon atoms in the molecule of which from about 13 carbon atoms to about 18 carbon atoms, and preferably at least 15 carbon atoms, are in a long chain. Such olefins can be obtained by the dehydrogenation of paratlins, such as by the cracking of paraffin waxes or by the dehalogenation of alkyl halides, preferably long chain alkyl halides, particularly halogenated parafiin waxes.

Also contemplated within the scope of the present invention are the reaction products of a phosphorus sulfide with an aromatic hydrocarbon, such as for example, benzene, naphthalene, toluene, xylene, diphenyl and the like or with an alkylated aromatic hydrocarbon, such as for example, benzene having an alkyl substituent having at least four carbon atoms, and preferably at least eight carbon atoms, such as long chain paraflin wax.

The phosphorus sulfide-hydrocarbon reaction product is prepared by reacting the phosphorus sulfide, e.g. P 8 with the hydrocarbon at a temperature of from about F. to about 600 F., preferably from about 300 F.

to about 500 F., using from 1% to about 50%, preferably from about 5% to about 25% of phosphorus sulfide; the reaction is carried out in from one to about ten hours. It is preferable to use an amount of the phosphorus sulfide that will completely react with the hydrocarbon so that no further purification is necessary; however, an excess of the phosphorus sulfide can be used, and the unreacted material separated by filtration. The reaction, if desired, can be carried out in the presence of a sulturizing agent such as sulfur or a halide of sulfur as described in U.S. 2,316,087, issued to J. W. Gaynor et a1. April 6, 1943. It is advantageous to maintain a non-oxidizing atmosphere, for example an atmosphere of nitrogen, in the reaction vessel. Under the above conditions, hydrolysis of the reaction product does not occur.

The complex of the unhydrolyzed reaction product of the phosphorus sulfide and the hydrocarbon is then formed by neutralization with a basic alkaline earth compound in the presence of a boron compound as above described, water and an alkanol at the reflux temperature of the alkanol. The basic alkaline earth compound can be for example the oxide, hydroxide, carbonate or sulfide of calcium, barium, strontium or magnesium, although barium oxide is preferred. While it is preferred to use boric acid, boric acid anhydride or a boric acid ester which decomposes to give boric acid can be used. The alkanol used can be methanol, ethanol, propanol or isopropanol, although methanol is preferred.

The formation of the complex can be carried out directly with the phosphorus sulfide-hydrocarbon reaction product; however, to facilitate handling, it is preferable to form a slurry of the unhydrolyzed phosphorus sulfidehydrocarbon reaction product by dilution with a lubricating oil, such for example, a 5W oil, although any suitable1 normally liquid hydrocarbon or oil diluent can be use The formation of the complex is suitably carried out by adding to the oil-diluted phosphorus sulfide-hydrocarbon reaction product from about 0.10 mol to about 3.0 mols of the boric acid, anhydride or ester per mole of phosphorus, and neutralizing the mixture with from about 1 mol to about 4 mols of the basic alkaline earth compound in the presence from 0.2 mol to 2.00 mols water and from about 1 mol to about 10 mols of the alkanol, per mol of the basic alkaline earth compound and heating the reaction mixture at a temperature of from about 100 F. to about 180 F., and preferably at the reflux temperature of the alkanol for a period of from about 1 hour to about 10 hours. The reaction vessel is equipped with a reflux condenser to avoid the loss of alkanol and water vapors. After heating at the 'reflux temperature for the required time, the temperature is raised to about 300 F. to 400 F. to remove water and alcohol and the product filtered through a suitable adsorbent material such as for example Celite, Attapulgus clay, fullers earth and the like. If desired, the alkalinity of the product can be reduced by blowing with CO or a C -containing gas. Products prepared in accordance with the present invention have alkaline earth to phosphorus ratios, that is ratios of from about 2:1 to about 15:1, respectively. The preferred products contain barium to phosphorus ratios of from about 5:1 to about 15:1 respectively.

The following specific examples illustrate the preparation of the herein described oil-soluble additive complex. It is to be understood that the examples are for the purpose of illustration only and are not to be regarded as a limitation of the present invention.

EXAMPLE I A butylene polymer having a molecular weight of about 750-800 was reacted with 15.5% (wt) P 8 at about 450 F. for about 5.5 hours. Fifteen hundred grams of the resultant product, having a phosphorus content of 2.3% and a sulfur content of 3.97% was diluted with 600 grams of an SAE-SW motor oil base.

A mixture of 2100 grams of the diluted reaction product (equivalent to 1.116 moles P) and 70 grams (1.13 moles) boric acid was neutralized with 245 grams (1.6 moles Ba) barium oxide in the presence of 23 ccs. water (0.8 m./m. BaO) and 450 ccs. methanol (7 m./m. BaO) at the reflux temperature of the methanol (about 160 F.) for 3 hours. The product was then heated to 320-350 F. to remove the methanol and water and filtered through Celite. The filtrate had an alkalinity of 31 mg. KOH per gram of product and contained 9.3% barium, 1.28% phosphorus, 2.4% and 0.5% boron.

EXAM PLE II A polybutene having an average molecular weight of about 780 and a Say-bolt Universal viscosity at 210 F. of about 1000 seconds was reacted with 15.5% (wt.) P S at 450 F. for about 5.5 hours; and the resultant reaction product contained 4.4% phosphorus and 7.7% sulfur. To a slurry of 250 gallons of this resultant product and 290 gallons of a solvent extracted SAE-SW mineral oil was added a slurry of 800 pounds of barium oxide (BaO) and 2.20 pounds of boric acid in 138 gallons of the solvent extracted SAB-SW mineral oil. To the foregoing mixture, cooled to F., a mixture of gallons methanol and 8 gallons of water was added at a rate to maintain the temperature of the reaction mixture below about 160 F., i.e. in the range of about 150 F. to 158 F.; about one hour was required for the addition of the methanol-water mixture. The reaction mixture was then refluxed for 3 hours at about F., the temperature then raised to 300-400 F. to remove the methanol and water, and the product filtered through Celite. The resultant filtrate which had a viscosity of 317 SUS at 210 F. contained 0.51% boron, 1.51% phosphorus, 2.43% sulfur, and 10.75% barium.

EXAMPLE III The process of Example 11 was modified by subjecting the neutralized product after heating at the reflux temperature to steaming for one hour while being heated to 280-310 F. prior to filtration. The resultant filtrate which had a viscosity of 275 SUS at 210 F. contained 0.49% boron, 1.44% phosphorus, 2.35% sulfur and 10.3% barium.

EXAMPLE IV A polybutene having an average molecular weight of about 780 was reacted with 15.5% P 8 at about 450 F. for 5-5Vz hours. 1170 grams of the resultant product was diluted with 500 grams of an SAE-SW motor oil base to give a slurry containing 0.87 mol total phosphorus. To the oil slurry were added 70 grams (1.13 moles) of boric acid and the mixture then neutralized with 85 grams (1.52 moles) calcium oxide in the presence of 400 cc. methanol and 4 cc. Water at the reflux temperature of the methanol (about 158 F.) for 3 hours. The product was then heated to 300 F. to remove the methanol and water and filtered through Celite. The recovered filtrate contained 1.38% phosphorus, 2.71 calcium, 0.54% boron and 2.37% sulfur.

The herein described additive of the present invention can be used in amounts of from about 0.01% to about 15%, preferably from about 0.25% to about 10% in lubricant base oils, such as mineral lubricating oils, synthetic hydrocarbon lubricating oils, synthetic lubricating oils of the polyalkylene oxide type, for example, the 'Ucon oils marketed by Carbide and Carbon Corporation, as well as polycarbox'ylic acid ester type synthetic lubricating oils such as the esters of adipic acid, sebacic acid, azelaic acid, etc. While the additive of the present invention can be used alone in the base oil, small amounts, e.g. 0.02% to 10%, of other lubricant addition agents, such as zinc dialkyl dithiophosphates, sulfurized terpene, e.g. sulfurized dipentene, viscosity index improvers, pour point depressors, rust inhibitors, etc.

. EXAMPLE'V A polybutene having an average molecular weight of about 780 was reacted with 15.5% P 8 at about 450 F. for 55'/2 hours, and the resultant reaction product diluted with an SAE-SW motor oil to give a diluted product containing 1.2% phosphorus. To 2000 grams of the diluted product were added 50 grams of boric acid and the mixture treated with 270 grams of BaO in the presence of 500 ccs. methanol (7 mols per mol BaO) and 24 cos. water (0.8 mol per mol BaO) at the reflux temperature of the methanol for 3 hours. The product was then heated to 320 F. to 350 F. to remove the methanol and water, and filtered through Celite. The recovered filtrate contained 1.0% phosphorus, 8.56% barium, 0.5% boron and 1.7% sulfur.

While in the above examples, polybutene has been used as the representative hydrocarbon in the reaction, other hydrocarbons, especially normally liquid hydrocarbons, can be used.

The effectiveness of the additives of the present invention in inhibiting corrosion toward copper and/or lead-containing metals, such as for example, copper-lead alloys, and their oxidation inhibiting properties, are demonstrated by the data in Table I, obtained by subjecting the above samples to the following test:

A copper-lead test specimen is lightly abraded with steel wool, washed with naphtha, dried and weighed to the nearest milligram. The cleaned copper-lead test specimen is suspended in a steel beaker, cleaned with a hot trisodium phosphate solution, rinsed with water, and acetone, and dried, and 250 grams of the oil to be tested together with 0.625 gram lead oxide and 50 grams of a 30-35 mesh sand charged to the beaker The beaker is then'plac'ed in a bath or heating block and heated to a temperature of 300 F. (i2 F.) while the contents are stirred by means of a stirrer rotating at 750 rpm. The contents of the beaker are maintained at this temperature for twenty-four hours, after which the copperlead test specimen is removed, rinsed with naphtha, dried and weighed. The test specimen is then replaced in the beaker and an additional 0.375 gram of lead oxide added to the test oil. At the end of an additional twenty-four hours of test operation the test specimen is again removed, rinsed, and dried as before and Weighed. The test specimen is again placed in the beaker together with an additional 0.250 gram of lead oxide and the test continued for another twenty-four hours (seventy-two hours total). At the conclusion of this time, the test specimen is removed from the beaker, rinsed in naphtha, dried and weighed. In addition to determining the weight loss of the metal specimen, the acidity of the oil in terms of milligrams of KOH per gram of oil is determined at the 24, 48, and 72 hour intervals. The loss in weight of the test specimen is recorded after each weighing.

This test, known as the sand stirring corrosion test, is referred to hereinafter as S.S.C.T."

The following samples were subjected to the above 168i:

Sample A-Solvent extracted SAE-30 mineral oil.

Sample B--A+4.3% of a barium-containing neutralized hydrolyzed reaction product of P 8 and a polybutene of about 800 molecular weight, containing 5.3% Ba, 2.04% P, and 1.17% S.

Sample CA+6.0% product of Example 1.

Sample D-A+6.0% product of Example I+0.3% sulfurized dipentene.

Sample EA+2.27% product of Example I+0.3% zinc dialkyl dithiophosphate.

Sample FA+6.0% product of Example I+0.3% zinc dialkyl dithiophosphate.

Sample G--A+6% product of Example IV.

Sample H--A+2.5% product of Example IV+0.3% sulfun'zed dipentene.

'6 Sample I-P+5.0% product of--Example IV.|0.3% sulfurized'dipentene. Sample IA+5.0% product of Example IV+0.3% zinc dialkyl dithiophosphate.

Table l- Acidity-mg. KOH/g. oil Wt. Loss- Total mgs. Sample 24 Hrs 48 Hrs. 12 Hrs. '48 Hrs. 72 Hrs.

5. 3 12. 6 1s. 6 734 1, 301 6.16 12. 04 16.80 698 1, 360 0. as 1.68 s. 7 19 an 0.28 1.68 4. 2 so 0. as 0.78 o. 92 2a 403 0. 2s 1. 4 1. as 21 41 0. s4 2. 52 11.0 48 45a 1. 12 3. as s. 72 54 147 1.12 2. 52 a. 92 4'6 65 1.12 2. 24 s. 12 as 1 Passn'ole weight losses are 200 milligram at 48 hours and 500 milligrams at 72 hours.

The additive of the present invention was subjected to several severe engine test procedures designated the Caterpillar L-l test and the L-4 test.

The L-l test designated to measure oil detergency is conducted in a 1AS1 single cylinder Caterpillar engine operating at 1000 r.p.m. at a load of 19.8 B.H.P., an oil sump temperature of l45-l50 F. and a water temperature of l75-l80 F. The test is run for 480 hours using a 1% sulfur S1 diesel fuel. At the end of each 120, 240 and 480 hours, inspections are made for carbon on the top ring groove, expressed in. terms of percent groove filling.

The L4 engine test, designed for evaluating the oxidation and bearing corrosion characteristics of motor oils, is conducted according to the procedure specified by the CRC designation L4545, CRC Handbook, 1946 edition,- Coordinating Lubricants Research Council, New York. Briefly, the test procedure involves the operation of ,a special six-cylinder automotive engine at constant speed and load for a period of 36 hours. The engine is operated at 3150 r.p.m.:25 at an engine load-of 30 B.H.P.:l with a jacket coolant outlet temperature of 200 F.i2 and an inlet temperature of F. min. Oil sump temperature of 265280 F. (depending on the base oil viscosity) is used. At the end of the test period, the engine is disassembled and inspected for .deposits and rated on a cleanliness scale of 0 to 10; a rating of 10 denoting a clean engine free of deposits. The bearings are weighed to determine the weight loss due to corrosion.

The following oil samples were tested in accordance with the above test procedures and the data obtained given in Table II.

Sample A--Solvent extracted petroleum SAE-30 base oil.

Sample B--A+4.5% (vol.) product of Example I.

Sangnle CB+0.24% (vol.) zinc dialkyl dithiophosp ate.

Sample D--A+2.24% product of Example I+0.3%

(vol). zinc dialkyl dithiophosphate.

Sample EA+2.24% product of Example I+0.4%

(vol.) zinc dialkyl dithiophosphate.

Sample F--A+2.24% product of Example I+0.35%

(vol.) zinc dialkyl dithiophosphate.

Sample GA+4.1% (vol.) product of Example l i-0.6%

zinc dialkyl dithiophosphate.

Sample H-A+4.5% (vol.) plant product prepared as in Example H.

Sample IA+3.5% (vol.) plant product 1 prepared as in Example II+0.62% (vol.) zinc dialkyl dithiophosphate.

0 Sample I--A+2.25% (vol.) plant product prepared as in Example II+0.35% (vol.) zinc dialkyl dithiophosphate.

Contained 1.4% 'P, 0.4% B, 2.18% S, 9.7% Ba.

Prepared from a mixture or isopropanol and methyl "0- butyl carblnol.

Iablc .1!

cent p Qroove 1: Re lt Detergency Carbon Sample Level w 240Hrs 480 Hrs. Bearing Varnish Wt. Loss Rating 1 Average of 3 values.

The silver and copper corrosion inhibiting properties of the present invention is demonstrated by the data obtained by the following test, designated the modified EMD test.

A silver or copper strip 2 cm. x 5.5. cm. with a small hol ato s a for uspens n, i l g y a r d t Nosteel wool, wiped free of any adhering steel wool, washed with carbon tetrachloride, airl-dried and then Weighed to 0,1 milligram. 300 cc. of the oil to be tested is placed in a 500 .cc. lipless glass beaker and the oil heated to a temperature of either 285 F. or 325 F. (:2 F.) depending on the desired test conditions and the silver or copper strip suspended in the oil so that the strip is completely immersed therein. The oil in the beaker is stirred by means .of a glass stirrer operating at 300 r.p.m. At the end of twenty-four hours, the silver or copper strip is removed, and while still hot, rinsed thoroughly with carbon tetrachloride and air-dried. The silver or copper strip is then immersed in a 10% potassium cyanide solution at room temperature until the surface of the test strip assumes its original bright appearance. The strip is then washed successively with distilled water and acetone, air-dried, weighed.

The following samples were subjected to the above test and the data obtained given in Table III:

ample A=S cn ex rac ed pet e m SA -39 m t oi ba ed-3.3% of a barium n sin r neu iz bydrolyzed rea ti n p od c of P2 5 and a po y u cn having average molecular weight of about 780, plus 5% zi c d alky sii h phc p Sample B..So lve nt extracted petroleum SAE-BO motor oil base=i=5.47% of the product of Example I.

Table III 235 F. 325 F Sample Ag Cu Ag Cu sired for the particular conditions of use-to give a finished product containing from 0.01% to about of the additive of the present invention.

Percentages given herein and in the appended claims are weight percentages unless otherwise stated.

Although the present invention has been described with reference to specific preferred embodiments thereof, the

invention is not to be considered as limited thereto but includes within its scope such modifications and variations as come the spirit of the appended claims.

We claim:

1. As a new composition of matter, the oil-soluble neutralized alkaline earth and boron-containing complex of the reaction product of a phosphorus sulfide and a normally non-gaseous hydrocarbon, said neutralized complex being obtained by the process comprising reacting from about 1% to about 50% of a phosphorus sulfide and a normally non-gaseous hydrocarbon at a temperature of from about 150 F. to about 500 F. undernonhydrolyzing conditions, adding from about 0.10 mol to about 3 mols of a horse compound selected from the group consisting of boric acid, boric acid anhydride and a boric acid ester per mol of phosphorus, neutralizing the resultant mixture with from'about 1 mol to about 4 mols of an inorganic basic alkaline earth compound in the presence of from about 0.20 mol to about 2 mols water and fromabout 1 mol to about 10 mols of an alkanol having not more than three carbon atoms, per mol of said basic alkaline earth compound while heating the mixture at a temperature of from about F. to about 180 F. under reflux conditions, for a period of from 1 hour to about 10 hours, raising the temperature of the mixture from about 300 F. to about 400 F. and filtering the resultant neutralized complex product.

2. A new composition of matter as described in claim n hic he bo o compoun i boric d- 3. A new com osition "or matter as described in claim 1 in which e Issue s nactb noil- 4. A new composition of matter as described in .1 in whi h t e ba i lka ne ea h c mpo nd i B b- A ne compositi n c m t e s dc ibcd in im 1 in which the basic alkaline earth compound is Cat).

6. As a new composition of matter the oil-soluble neura z d b i and bor n-c n a ning mp ex of the rection p od ct o a ph spho us u fide and n cl n pci ym r. on complex be n btained y t p oc ss compri ng reac ing rcrn a out-1% o about 50% of a Ph Phcru sulfi e i h n olefi po yme a a empe at e of f om bou F- to ab ut 500 under n n-hyly i g ondi ons, add ng from a ou 0 1 mp o abc t 3 lmcls b ic ac d to th resultant reac n p oduc pe l of pho pho us. ne tra iz g he m x u e with r m bout 1 mol to about 4 mols ba um de in the presence of from about 0.20 mol to about 2 mols water and from about 1 mol to about 10 mols methanol, per mol of barium oxide while heating the mixture at the fl x mpe t re of m thano f a P io of from abou 1 hour to about 10 hours, raising the temperature of the mixture to from a o t 300 F. to a o 0 a fi e ins he r sul an n tr d comp x p d c '7. A new composition of matter as described in claim 6 in which the olefin polymer is a polybutene.

8. A lubricant composition comprising a major proportion of a normally liquid oleaginous lubricant and from about 0.01% to about 15% or the oil-soluble neutralized alkaline earth and boron-containing complex of the reaction product of a phosphorus sulfide and a normally n nseous hydroca b n s 0 11 1 being bainc by t e pr s c p sin a n fr m a o 1% to about 50% of a phosphorus sulfide and a normally non-gaseous hydrocarbon at a temperature of from about 150 F. to about 500 'F. under non-hydrolyzing conditions, adding from about 0.10 mol to about 3 mols of a boron compound selected from the group consisting of boric acid, boric acid anhydride and a boric acid ester, per mol of phosphorus, neutralizing the resultant mixture with from about 1 mol to about 4 mols of an inorganic basic alkaline earth compound in the presence of from about 0.20 mol to about 2.00 mols water and from about 1 mol to about '1 m ls of an alkanol h ving not mere t an ca bon s ems, pe m of s id basic alkaline earth compound, while heating the mixture at 9 a temperature of from about 100 F. to about 180 F. under reflux conditions for a period of from 1 hour to hours, raising the temperature of the mixture to from about 300 F. to about 400 F. and filtering the resultant heated neutralized product.

'9. A lubricant composition as described in claim 8 in which the boron compound is boric acid.

40. A lubricant composition as described in claim 8 in which the alkanol is methanol.

11. IA lubricant composition as described in claim 8 in which the basic alkaline earth compound is BaO.

12. A lubricant composition as described in claim 8 in which the basic alkaline earth compound is CaO.

13. A lubricant composition comprising a major proportion of a hydrocarbon lubricating oil and from about 0.01% to about of the oil-soluble neutralized barium and boron-containing reaction product of a phosphorus sulfide and an olefin polymer, said neutralized product being obtained by the process comprising reacting from about 1% to about 50% of a phosphorus sulfide with an olefin polymer at a temperature of from about 150 F. to about 500 F. under non-hydrolyzing conditions, adding from about 0.10 mol to about 3 mols boric acid to the resultant reaction product, neutralizing the mixture with from about 1 mol to about 4 mols barium oxide in the presence of from about 0.20 mol to about 2.00 mols water and from about 1 mol to about 10 mols methanol, per mol of the barium oxide, while heating the mixture at the reflux temperature of methanol for a period of from about 1 hour to about 10 hours, raising the temperature of the mixture to from about 320 F. to about 350 F. and filtering the resultant neutralized product.

14. A lubricant composition as described in claim 13 in which the olefin polymer is a polybutene.

15. An addition agent concentrate for lubricating oils consisting essentially of a lubricating oil containing more than 15% of an oil-soluble neutralized alkaline earth and boron-containing complex of the reaction product of a phosphorus sulfide and a normally non-gaseous hydrocarbon, said neutralized complex being obtained by the process comprising reacting from about 1% to about of a phosphorus sulfide and a normally non-gaseous hydrocarbon at a temperature of from about F. to about 500 F., under non-hydrolyzing conditions, neutralizing the resultant unhyd'rolyzed reaction product with from about 1 mol to about 4 mols of an inorganic basic alkaline earth compound in the presence of from about 0.10 mol to about 3 mols of a boron compound selected from the group consisting of boric acid, boric acid anhydride and a boric acid ester, per mol of phosphorus, from about 0.20 mol to about 2.00 mols water and from about 1 mol to about 10 mols of an alkanol having not more than three carbon atoms, per mol of said basic alkaline earth compound while heating the mixture at a temperature of from about 100 F. to about 180 F. under reflux conditions for a period of from 1 hour to about 10 hours, raising the temperature of the mixture from about 300 F. to about 400 F. and filtering the resultant neutralized complex product, said concentrate being capable of dilution with a lubrication oil to form a homogeneous mixture containing from about 0.01% to about 15 of said complex.

References fitted in the of this patent UNITED STATES PATENTS 2,053,474 Graves et al Sept. 8, 1936- 2,346,156 Farrington et al Apr. 11, 1944' 2,688,612 Watson Sept. 7, 1954 2,851,416 Sabol et al. Sept. '9, 1958 2,900,376 Sabol et a1 Aug. 18, 1959 

1. AS A NEW COMPOSITION OF MATTER, THE OIL-SOLUBLE NEUTRALIZED ALKALINE EARTH AND BORON-CONTAINING COMPLEX OF THE REACTION PRODUCT OF A PHOSPHORUS SULFIDE AND A NORMALLY NON-GASEOUS HYDROCARBON, SAID NEUTRALIZED COMPLEX BEING OBTAINED BY THE PROCESS COMPRISING REACTING FROM ABOUT 1% TO ABOUT 50% OF A PHOSPHORUS SULFIDE AND A NORMALLY NON-GASEOUS HYDROCARBON AT A TEMPERATURE OF FROM ABOUT 150*F. TO ABOUT 500*F. UNDER NONHYDROLYZING CONDITIONS, ADDING FROM ABOUT 0.10 MOL TO ABOUT 3 MOLS OF A BORON COMPOUND SELECTED FROM THE GROUP CONSISTING OF BORIC ACID, BORIC ACID ANHYDRIDE AND A BORIC ACID ESTER PER MOL OF PHOSPHORUS, NEUTRALIZING THE RESULTANT MIXTURE WITH FROM ABOUT 1 MOL TO ABOUT 4 MOLS OF AN INORGANIC BASIC ALKALINE EARTH COMPOUND IN THE PRESENCE OF FROM ABOUT 0.20 MOL TO ABOUT 2 MOLS WATER AND FROM ABOUT 1 MOL TO ABOUT 10 MOLS OF AN ALKANOL HAVING NOT MORE THAN THREE CARBON ATOMS, PER MOL OF SAID BASIC ALKALINE EARTH COMPOUND WHILE HEATING THE MIXTURE AT A TEMPERATURE OF FROM ABOUT 100*F. TO ABOUT 180*F. UNDER REFLUX CONDITIONS, FOR A PERIOD OF FROM 1 HOUR TO ABOUT 10 HOURS, RAISING THE TEMPERATURE OF THE MIXTURE FROM ABOUT 300*F. TO ABOUT 400*F. AND FILTERING THE RESULTANT NEUTRALIZED COMPLEX PRODUCT. 